Allylic amines are versatile building blocks in organic synthesis and exist in bioactive compounds, but their synthesis via hydroaminoalkylation of alkynes with amines has been a formidable challenge. Here, we report a late transition metal Ni-catalyzed hydroaminoalkylation of alkynes with N-sulfonyl amines, providing a series of allylic amines in up to 94% yield. Double ligands of N-heterocyclic carbene (IPr) and tricyclohexylphosphine (PCy) effectively promote the reaction.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8217523 | PMC |
http://dx.doi.org/10.1038/s41467-021-24032-9 | DOI Listing |
J Am Chem Soc
July 2022
Department of Chemistry, The University of British Columbia, Vancouver, BC, Canada, V6T 1Z1.
Hydroaminoalkylation is a powerful, atom-economic catalytic reaction for the reaction of amines with alkenes and alkynes. This C-H functionalization reaction allows for the atom-economic alkylation of amines using simple alkenes or alkynes as the alkylating agents. This transformation has significant potential for transformative approaches in the pharmaceutical, agrochemical, and fine chemical industries in the preparation of selectively substituted amines and -heterocycles and shows promise in materials science for the synthesis of functional and responsive aminated materials.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2022
University of Vienna, Institute of Organic Chemistry, Währinger Strasse 38, 1090, Vienna, Austria.
The development of reactions converting alkenes and alkynes into valuable building blocks remains one of the main goals of synthetic chemistry. Herein, we present the leveraging of highly electron-deficient iminium ions, rare and fleeting intermediates, into a general amine synthesis. This enables the preparation of amines bearing e.
View Article and Find Full Text PDFChemistry
February 2022
Institut für Chemie, Universität Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26129, Oldenburg, Germany.
Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn , Ph C[B(C F ) ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary β,γ-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.
View Article and Find Full Text PDFNat Commun
June 2021
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, China.
Allylic amines are versatile building blocks in organic synthesis and exist in bioactive compounds, but their synthesis via hydroaminoalkylation of alkynes with amines has been a formidable challenge. Here, we report a late transition metal Ni-catalyzed hydroaminoalkylation of alkynes with N-sulfonyl amines, providing a series of allylic amines in up to 94% yield. Double ligands of N-heterocyclic carbene (IPr) and tricyclohexylphosphine (PCy) effectively promote the reaction.
View Article and Find Full Text PDFChemistry
April 2021
Institut für Chemie, Universität Oldenburg, Carl-von-Ossietzky-Strasse 9-11, 26129, Oldenburg, Germany.
Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl- and dialkylalkynes as well as a terminal alkyne take place with N-benzylanilines, N-alkylanilines, and N-alkylbenzylamines.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!